Deprotonation of a hydrophosphorane and synthesis of the Ni(II) metallophosphorane [NiCl{P(OC6H4N(CH3))2}(P(CH3)3)2]

被引：7

作者：

Jelier, Benson J. ^{[2
]}

Montgomery, Craig D. ^{[1
]}

Parlane, Fraser G. L. ^{[1
]}

机构：

[1] Trinity Western Univ, Dept Chem, Langley, BC V2Y 1Y1, Canada

[2] Simon Fraser Univ, Dept Chem, Burnaby, BC V5A 1S6, Canada

来源：

INORGANICA CHIMICA ACTA | 2014年 / 413卷

关键词：

Phosphorane; Pentacoordination; Nickel complexes; pi-Bonding; X-ray crystal structure; Density Functional Theory; X-RAY CRYSTAL; MOLECULAR-STRUCTURE; TRANSFORMATION MECHANISM; NUCLEOPHILIC-ATTACK; 1ST ISOLATIONS; PHOSPHORANIDE; COMPLEX; LIGANDS; PLATINUM(II); CHEMISTRY;

D O I：

10.1016/j.ica.2013.12.042

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The hydrophosphorane [HP(OC6H4N(CH3))(2)] has been deprotonated using lithium tetramethylpiperidide to produce Li[P(OC6H4N(CH3))(2)] (1). Compound 1 reacts further with NiCl2(PMe3)(2) to form the Ni(II) phosphoranide complex [NiCl{P(OC6H4N(CH3))(2)}(P(CH3)(3))(2)] (2). The crystal structures of both 1 and 2 were determined. The structure of 1 is dimeric with bridging lithium cations and also features one THF solvent molecule coordinated to each lithium cation; the geometry about the lithium atom is tetrahedral. The structure of 2 displays tetrahedral distortion from an idealized square-planar geometry. Both 1 and 2 characterized by H-1 and P-31 NMR, with C-13 NMR for 2 also. DFT calculations (B3LYP/6311++G(2df,2p)) were also done on 2; both the NMR and DFT studies indicate p-donation from the metal to the pentacoordinate phosphorus. (C) 2014 Elsevier B.V. All rights reserved.

引用

页码：121 / 127

页数：7

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